4-propylaniline complexes with one and two argon atoms formed in the molecular beam were studied in the first excited electronic state, S1, using resonance enhanced two-photon ionization spectroscopy and in the cation ground state, D0, using mass analyzed threshold ionization spectroscopy. The combination of electronic and cationic spectra of the clusters allows two conformations to be identified in both aniline-Ar1 and aniline-Ar2, which are assigned to either the gauche configuration or anti-configuration of 4-propylaniline. The gauche isomer exhibits complex bands shifted 29 cm−1 and 89 cm−1 from the S1 origin bands and 83 cm−1 and 148 cm−1 from the ionization potential assigned to the Ar1 and Ar2 complexes, respectively. For the anti-rotamer, the corresponding shifts actually become nearly additive, 53 cm−1 and 109 cm−1 for the S1 origin bands, and 61 cm−1 and 125 cm−1 for the ionization potentials. Ab initio calculations provide insights into the influences of the propyl and amino groups on the positions of the argon atoms within the clusters. In addition, the binding energy of one argon with the gauche isomer of 4-propylaniline has been measured to be 550 ± 5 cm−1 in the D0 state, 496 ± 5 cm−1 in the S1 state, and 467 ± 5 cm−1 in the neutral ground state, S0.

1.
P. E. S.
Wormer
and
A.
van der Avoird
,
Chem. Rev.
100
,
4109
(
2000
).
2.
P.
Hobza
and
K.
Muller-Dethlefs
,
Non-Covalent Interactions
(
Royal Society of Chemistry
,
Cambridge
,
2009
).
3.
L.
Béguin
,
A.
Vernier
,
R.
Chicireanu
,
T.
Lahaye
, and
A.
Browaeys
,
Phys. Rev. Lett.
110
,
263201
(
2013
).
4.
Th.
Weber
,
A.
von Bargen
,
E.
Riedle
, and
H. J.
Neusser
,
J. Chem. Phys.
92
,
90
(
1990
);
A.
Dullweber
,
M. P.
Hodges
, and
D. J.
Wales
,
J. Chem. Phys.
106
,
1530
(
1997
);
W.
Kim
and
P. M.
Felker
,
J. Chem. Phys.
107
,
2193
(
1997
).
5.
R. G.
Satink
,
H.
Piest
,
G.
von helden
, and
G.
Meijer
,
J. Chem. Phys.
111
,
10750
(
1999
).
6.
M.
Mons
,
J.
Le Calvé
,
F.
Piuzzi
, and
I.
Dimicoli
,
J. Chem. Phys.
92
,
2155
(
1990
);
J.
Makarewicz
,
J. Chem. Phys.
124
,
084310
(
2006
);
[PubMed]
M. A.
Vincent
,
I. H.
Hillier
,
C. A.
Morgado
,
N. A.
Burton
, and
X.
Shan
,
J. Chem. Phys.
128
,
044313
(
2008
).
[PubMed]
7.
X.
Zhang
,
J. M.
Smith
, and
J. L.
Knee
,
J. Chem. Phys.
97
,
2843
(
1992
).
8.
E.
Shalev
,
N.
Ben-Horin
,
U.
Even
, and
J.
Jortner
,
J. Chem. Phys.
95
,
3147
(
1996
).
9.
C.
Crepin
and
A.
Trarner
,
Chem. Phys. Lett.
170
,
446
(
1990
).
10.
H. C.
Longuet-Higgins
and
J. A.
Pople
,
J. Chem. Phys.
27
,
192
(
1957
).
11.
P.
Hobza
,
O.
Bludský
,
H. L.
Selzle
, and
E. W.
Schlag
,
J. Chem. Phys.
97
,
335
(
1992
);
O.
Bludský
,
V.
Špirko
,
V.
Hrouda
, and
P.
Hobza
,
Chem. Phys. Lett.
196
,
410
(
1992
).
12.
B.
Fernández
,
H.
Koch
, and
J.
Makarewicz
,
J. Chem. Phys.
111
,
5922
(
1999
).
13.
H.
Koch
,
B.
Fernández
, and
J.
Makarewicz
,
J. Chem. Phys.
111
,
198
(
1999
).
14.
P.
Tarakeshwar
,
K. S.
Kim
,
E.
Kraka
, and
D.
Cremer
,
J. Chem. Phys.
115
,
6018
(
2001
).
15.
N.
Solcà
and
O.
Dopfer
,
Eur. Phys. J.
D 20
,
469
480
(
2002
);
S.
Ishiuchi
,
M.
Sakai
,
Y.
Tsuchida
,
A.
Takeda
,
Y.
Kawashima
,
O.
Dopfer
,
K.
Müller-Dethlefs
, and
M.
Fujii
,
J. Chem. Phys.
127
,
114307
(
2007
);
[PubMed]
M.
Fujii
and
O.
Dopfer
,
Int. Rev. Phys. Chem.
31
,
131
173
(
2012
).
16.
J.
Cerný
,
X.
Tong
,
P.
Hobza
, and
K.
Müller-Detlefs
,
J. Chem. Phys.
128
,
114319
(
2008
).
17.
I.
Kalkman
,
C.
Brand
,
T.-B. C.
Vu
,
W. L.
Meerts
,
Y. N.
Svartsov
,
O.
Dopfer
,
X.
Tong
,
K.
Muller-Dethlefs
,
S.
Grimme
, and
M.
Schmitt
,
J. Chem. Phys.
130
,
224303
(
2009
).
18.
I.
López-Tocón
,
J. C.
Otero
,
M.
Becucci
,
G.
Pietraperzia
, and
E.
Castellucci
,
Chem. Phys.
249
,
113
(
1999
).
19.
D. G.
Lister
,
J. K.
Tyler
,
J. H.
Hog
, and
N. W.
Larsen
,
J. Mol. Struct.
23
,
253
(
1974
).
20.
W.
Sinclair
and
D.
Pratt
,
J. Chem. Phys.
105
,
7942
(
1996
).
21.
J.
Makarewicz
,
J. Phys. Chem. A
111
,
1498
(
2007
).
22.
P.
Parneix
and
P.
Bréchignac
,
J. Chem. Phys.
108
,
1932
(
1998
).
23.
T. M.
Korter
,
D. R.
Borst
,
C. J.
Butler
, and
D. W.
Pratt
,
J. Am. Chem. Soc.
123
,
96
(
2001
).
24.
K.
Kimura
,
J. Electron Spectrosc. Relat. Phenom.
108
,
31
(
2000
).
25.
T.
Pino
,
P.
Parneix
,
S.
Douin
, and
P.
Brechignac
,
J. Phys. Chem. A
108
,
7364
(
2004
).
26.
M.
Takahashi
,
H.
Ozeki
, and
K.
Kimura
,
J. Chem. Phys.
96
,
6399
(
1992
).
27.
S.
Douin
,
S.
Piccirillo
, and
P.
Brechignac
,
Chem. Phys. Lett.
273
,
389
(
1997
).
28.
X.
Song
,
E. R.
Davidson
,
S. R.
Gwaltney
, and
J. P.
Reilly
,
J. Chem. Phys.
100
,
5411
(
1994
).
29.
L. C.
Zhu
and
P.
Johnson
,
J. Chem. Phys.
94
,
5769
(
1991
);
X.
Zhang
,
J. D.
Pitts
,
R.
Nadarajah
, and
J. L.
Knee
,
J. Chem. Phys.
107
,
8239
(
1997
);
J. E.
Braun
,
T. L.
Grebner
, and
H. J.
Neusser
,
J. Phys. Chem. A
102
,
3273
(
1998
);
C. E. H.
Dessent
and
K.
Müller-Dethlefs
,
Chem. Rev.
100
,
3999
(
2000
);
[PubMed]
D. S.
Yang
,
J. Phys. Chem. Lett.
2
,
25
(
2011
).
[PubMed]
30.
S.
Basu
and
J. L.
Knee
,
J. Chem. Phys.
120
,
5631
(
2004
);
[PubMed]
Z.
Yang
,
Q.
Gu
,
C.
Trindle
, and
J. L.
Knee
,
J. Chem. Phys.
139
,
151101
(
2013
);
[PubMed]
Q.
Gu
,
C.
Trindle
, and
J. L.
Knee
,
J. Phys. Chem. A
118
,
4982
(
2014
).
[PubMed]
31.
H. J.
Dietrich
,
R.
Lindner
, and
K.
Mullerdethlefs
,
J. Chem. Phys.
101
,
3399
(
1994
).
32.
J. E.
Braun
and
H. J.
Neusser
,
Mass Spectrom. Rev.
21
,
16
(
2002
).
33.
Q.
Gu
and
J. L.
Knee
,
J. Chem. Phys.
128
,
064311
(
2008
).
34.
A. D.
Becke
,
J. Chem, Phys.
134
,
18A301
(
2014
).
35.
L.
Goerigk
and
S.
Grimme
,
Phys. Chem. Chem. Phys.
13
,
6670
(
2011
).
36.
L. A.
Burns
,
A.
Vasquez-Mayagoitia
,
B. G.
Sumpter
, and
C. D.
Sherrill
,
J. Chem. Phys.
134
,
0844107
(
2011
).
37.
A.
Li
,
H. S.
Muddana
, and
M. K.
Gilson
,
J. Chem. Theory Comput.
10
,
1563
(
2014
).
38.
M. J. T.
Frisch
,
G. W.
Trucks
,
H.B.
Schlegel
 et al, gaussian 09, Revision A.02 (Gaussian Inc., Wallingford, CT, 2009).
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